(PNSiMe3)4(NMe)6: A Robust Tetravalent Phosphaza‐adamantane Scaffold for Molecular and Macromolecular Construction

Tetraarylmethanes and adamantanes are important rigid covalent connectors that play a four‐way scaffolding role in molecular and materials chemistry. We report the synthesis of a new tetravalent phosphaza‐adamantane cage, (PNSiMe3)4(NMe)6 (2), that shows high thermal, air, and redox stability due to its geometry. It nevertheless participates in covalent four‐fold functionalization reactions along its periphery. The combination of a robust core and reactive corona makes 2 a convenient inorganic scaffold upon which tetrahedral molecular and macromolecular chemistry can be constructed. This potential is demonstrated by the synthesis of a tetrakis(bis(phosphine)iminium) ion (in compound 3) and the first all P/N poly(phosphazene) network (5). The synthesis of a new air‐stable and thermally robust tetrahedral tetravalent inorganic cage, (PNSiMe3)4(NMe)6 has been achieved. This cage allows four‐fold functionalization reactions on its periphery to give unprecedented molecular and macromolecular constructs. This utility is shown by the synthesis of a tetrakis(bis(phosphine)iminium) ion and the first all P/N polyphazene network material.